Triarylamine compounds, compositions and uses therefor

ABSTRACT

The present invention relates to triarylamine compounds, compositions comprising such compounds, and electronic devices and applications comprising at least one layer containing at least one of the new compounds. The compounds can be used as monomers to create homopolymers or copolymers.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to triarylamine compounds useful as chargetransport materials in electronic devices and other applications.

2. Background

In organic photoactive electronic devices, such as organic lightemitting diodes (“OLED”), that make up OLED displays, the organic activelayer is sandwiched between two electrical contact layers in an OLEDdisplay. In an OLED the organic photoactive layer emits light throughthe light-transmitting electrical contact layer upon application of avoltage across the electrical contact layers.

It is well known to use organic electroluminescent compounds as theactive component in light-emitting diodes. Simple organic molecules,conjugated polymers, and organometallic complexes have been used.

Devices that use photoactive materials frequently include one or morecharge transport layers, which are positioned between a photoactive(e.g., light-emitting) layer and a contact layer (hole-injecting contactlayer). A device can contain two or more contact layers. A holetransport layer can be positioned between the photoactive layer and thehole-injecting contact layer. The hole-injecting contact layer may alsobe called the anode. An electron transport layer can be positionedbetween the photoactive layer and the electron-injecting contact layer.The electron-injecting contact layer may also be called the cathode.

There is a continuing need for charge transport materials for use inelectronic devices and other applications.

SUMMARY OF THE INVENTION

One aspect of the invention is a new triarylamine compounds havingFormula I or III:

wherein

n is an integer of at least 1,

R¹ is selected from aryl, heteroaryl, fluoroaryl, and fluoroheteroaryland wherein R¹ may be same or different in each occurrence,

R³ is selected from H and R¹. R² is selected from H, R¹, alkyl,fluoroalkyl, Cl, Br, I and an arylamino group of Formula (II),

wherein R⁴ is selected from aryl, H, R¹, alkyl, and fluoroalkyl,

R⁷ is selected from aryl, heteroaryl, fluoroaryl, and fluoroheteroaryl,

E is selected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of 1 to20, (CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, and combinationsthereof, and can be different at each occurrence, wherein R⁵ and R⁶ areeach independently selected from H, F, alkyl, aryl, alkoxy, aryloxy,fluoroalkyl, fluoroaryl, fluoroalkoxy, and fluoroaryloxy and wherein R⁵and R⁶ can, when taken together, form a non-aromatic ring, provided thatwhen E is (CR⁵R⁶)_(m) and n is greater than 1 and m is 1, at least oneof R⁵ and R⁶ is not hydrogen or a hydrocarbon.

Also provided are polymers and copolymers prepared by polymerizingfunctional monomers having the Formula (I) or (III) as definedhereinabove.

Other aspects of the present invention include electronic devices andother applications having at least one layer comprising at least onecompound described above.

In another aspect of the present invention, compositions comprising atleast one of the above compounds are provided. Liquid compositionsincluding at least one compound described herein can be in the form of asolution, dispersion or emulsion.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims.

DESCRIPTION OF THE DRAWINGS

The invention is illustrated by way of example and not limitation in theaccompanying figures.

FIG. 1: An illustrative example of one organic electronic devicecomprising at least one layer comprising at least one of the newcompounds disclosed herein.

DETAILED DESCRIPTION OF THE EMBODIMENTS

The present invention provides new compounds, new methods of making saidcompounds, compositions comprising at least one of the new compounds,electronic devices and other applications comprising at least one layercomprising at least one of the new compounds, and methods for makingdevices containing the compounds. One aspect of the present arecompounds having Formula I or III:

wherein

n is an integer of at least 1

R¹ is selected from aryl, heteroaryl, fluoroaryl, and fluoroheteroaryland wherein the R¹ may be same or different in each occurrence,

R³ is selected from H and R¹,

R² is selected from H, R¹, alkyl, fluoroalkyl, Cl, Br, I and anarylamino group of formula (II),

R⁴ is selected from aryl, H, R¹, alkyl, and fluoroalkyl,

R⁷ is selected from aryl, heteroaryl, fluoroaryl, and fluoroheteroaryl,

E is selected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of 1 to20, (CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, and combinationsthereof, and can be different at each occurrence, wherein R⁵ and R⁶ areeach independently selected from H, F, alkyl, aryl, alkoxy, aryloxy,fluoroalkyl, fluoroaryl, fluoroalkoxy, and fluoroaryloxy and wherein R⁵and R⁶ can, when taken together, form a non-aromatic ring, provided thatwhen E is (CR⁵R⁶)_(m), and n is greater than 1 and m is 1, at least oneof R⁵ and R⁶ is not hydrogen or a hydrocarbon.

In some embodiments, at least one aromatic ring in the compound offormula (I) and III has one or more substituents independently selectedfrom H, F, alkyl, aryl, alkoxy, aryloxy, fluoroalkyl, fluoroaryl,fluoroalkoxy, and fluoroaryloxy. In further embodiments, substituents ontwo neighboring aromatic rings in the compound of formula (I) and IIIcan together form an aromatic or non-aromatic ring. In furtherembodiments, adjacent substituents on a single ring can be linked toform a fused aromatic or non-aromatic ring.

In some embodiments R¹ is aryl.

In some embodiments, R¹ is selected from phenyl, 1-naphthyl, and2-naphthyl. In some embodiments, n=1, R² is H, and R³ is selected fromphenyl, 1-naphthyl, and 2-naphthyl.

In some embodiment, R¹ is selected from fluoroaryl and fluoroheteroaryl,where the groups can have up to 7 fluorine atoms.

In some embodiments, R² is H or aryl. In some embodiments, R² isdifferent from R³. In some embodiments, R² is H and R³ is aryl.

In some embodiments, R⁴ is aryl.

In some embodiment, R⁷ is selected from fluoroaryl and fluoroheteroaryl,where the groups can have up to 7 fluorine atoms.

In one embodiment, the new compounds have Formula IV

wherein

n is an integer of at least 1, R¹ is selected from aryl, heteroaryl,fluoroaryl, and fluoroheteroaryl (wherein the fluoroaryl andfluoroheteroaryl is substituted with one or more fluorine atoms and insome embodiments up to 7 fluorine atoms), and R¹ may be different ateach occurrence. In some embodiments, R¹ is aryl. R² is selected from H,R¹, alkyl, fluoroalkyl, arylamino of formula (II), Cl, Br, I. In someembodiments, R² is H. R³ is selected from H and R¹. In some embodiments,R³ is aryl. R⁴ is selected from aryl, H, R¹, alkyl, fluoroalkyl. In someembodiments R⁴ is aryl. In some embodiments, R² is different from R³. Insome embodiments, R² is H and R³ is aryl.

E is selected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of 1 to20, (CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, and combinationsthereof, and can be different at each occurrence, wherein R⁵ and R⁶ areeach independently selected from H, F, alkyl, aryl, alkoxy, aryloxy,fluoroalkyl, fluoroaryl, fluoroalkoxy, and fluoroaryloxy and wherein R⁵and R⁶ can, when taken together, form a non-aromatic ring, provided thatwhen E is (CR⁵R⁶)_(m), and n is greater than 1 and m is 1, at least oneof R⁵ and R⁶ is not hydrogen or a hydrocarbon.

In some embodiments, at least one aromatic ring in the compound ofFormula (IV) has a substituent selected from H, F, alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fluoroaryl, fluoroalkoxy, and fluoroaryloxy.

In some embodiments, R¹ is selected from phenyl, 1-naphthyl, and2-naphthyl. In some embodiments, n=1, R² is H, and R³ is selected fromphenyl, 1-naphthyl, and 2-naphthyl.

Polymers and copolymers can be prepared by polymerizing multiplefunctional monomers having the Formulae I, III, and IV, wherein themonomer may be the same or different. As used herein, the term“functional monomer” is intended to mean a compound having at leastreactive group, and being capable of reacting with other compoundshaving the same or different reactive groups.

The practical upper limit of n in Formulae (I), (III) and (IV) isdetermined in part by the desired solubility of a compound in aparticular solvent or class of solvents. As the value of n increases,the molecular weight of the compound increases. The increase inmolecular weight is generally expected to result in a reduced solubilityof the compound in a particular solvent. Moreover, in one embodiment,the value of n at which a compound becomes substantially insoluble in agiven solvent is dependent in part upon the structure of the compound.For example, a compound containing multiple phenyl groups may becomesubstantially insoluble in an organic solvent when n is much less thanabout 10⁴. As another example, a compound containing fewer phenyl groupsand/or phenyl groups with particular functional groups may be soluble ina given solvent even though n is about 10⁴ or greater, even 10⁵ or 10⁶.The selection of the value of n and a solvent is within the purview ofone skilled in the art.

Also provided are compounds comprising copolymers prepared by combiningmultiple functional monomers of the compounds described herein. Suchmonomers can be grouped into three classes as follows:

Where y is an integer equal to or greater than 1 and w is zero or aninteger equal to or greater than one, and X is Cl, Br, I, boronic acid,boronic acid ester, boranes or a triflate group; and wherein X can bedifferent at each occurrence such that carbon-carbon (for Group 1) andcarbon-nitrogen bonds (for Groups 2 and 3) can be formed.

For convenience, exemplary monomers are assigned herein to Group 1,Group 2 or Group 3, and within the Groups, exemplary monomers areassigned to Subgroups such as, for example, within Group 1, subgroupsA1, A2, B, C1, C2, and C3.

Homopolymers and copolymers can be made using one or more monomers fromeach of subgroups within each of Group 1, Group 2, and/or Group 3,provided that no copolymers containing only monomers from subgroups A orcopolymers containing only monomers from subgroup B are obtained.Copolymers made from monomers within Group 3 contain at least onecomonomer designated A1 or A2, and at least one comonomer from subgroupE1, E2, E3, E4 and E5. Exemplary copolymers include poly(A-co-B);poly(A-co-C); poly(A-co-B-co-C); poly(A-co-C); and copolymers comprisingtwo or more monomers within group C, wherein, for example, “poly(A-co-B)” refers to a copolymer comprising, as polymerized units,monomers in Group A and monomers in Group B. The monomers, e.g., A andB, in such copolymers, can be present in equimolar ratios or innon-equimolar ratios. Copolymers made from monomers in Group 1 are madeby formation of carbon-carbon bonds during polymerization. Copolymersmade from monomers in Groups 2 and Groups 3 are made by formation ofcarbon-nitrogen bonds during polymerization.

The homopolymers and copolymers from Group 1 can generally be preparedusing known synthetic methods. In one synthetic method, as described inYamamoto, Progress in Polymer Science, Vol. 17, p 1153 (1992), thedihalo derivatives of the monomeric units are reacted with astoichiometric amount of a zerovalent nickel compound, such asbis(1,5-cyclooctadiene)nickel(0). In another method, as described inColon et al., Journal of Polymer Science, Part A, Polymer chemistry,Edition, Vol. 28, p. 367 (1990), the dihalo derivatives of the monomericunits are reacted with catalytic amounts of Ni(II) compounds in thepresence of stoichiometric amounts of a material capable of reducing thedivalent nickel ion to zerovalent nickel. Suitable materials includezinc, magnesium, calcium and lithium. In the third synthetic method, asdescribed in U.S. Pat. No. 5,962,631, and published PCT application WO00/53565, a dihalo derivative of one monomeric unit is reacted with aderivative of another monomeric unit having two reactive groups selectedfrom boronic acid, boronic acid esters, and boranes, in the presence ofa zerovalent palladium catalyst, such as tetrakis(triphenylphosphine)Pd.

Homopolymers and copolymers from Groups 2 and 3 can generally beprepared by Pd-catalyzed amination reactions. For example, homopolymersor copolymers containing monomers from Group 2 can be formed by reactinga monomer unit having both a reactive primary or secondary amine and areactive aryl halide in the presence of copper, nickel or palladiumcatalysts. Homopolymers or copolymers containing monomers from Group 3can be produced by the reaction of one or more dihalo monomericderivative(s) with one or more diamino (primary or secondary) monomericunit(s) in the presence of copper, nickel or palladium catalysts.Typical conditions for Pd-catalyzed amination reactions are described inSadighi, J. P.; Singer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998,120, 4960; Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald,S. L. J., Org. Chem. 200, 65, 1158; Hartwig, J. F.; Modern AreneChemistry 2002, 107-168, Astruc, D., Editor, Wiley-VCH Verlag GmbH & Co.KGaA, Weinheim, Germany. Typical conditions for Ni-catalyzed aminationreactions are described in Desmarets, C.; Schneider, R.; Fort, Y.Tetrahedron, 2001, 57, 6054; Wolfe, J. P.; Buchwald, S. L., J. Am. Chem.Soc. 1997, 119, 4960. Typical conditions for Cu-catalyzed aminationreactions are described in Klapars, A.; Antilla, J. C.; Huang, X.;Buchwald, S. L., J. Am. Chem. Soc. 2001, 123, 7727.

Polymers of the compounds disclosed herein can have improved thermalstability in comparison to, e.g., NPD and TPD. For example, a compoundof Formula IV wherein R¹ is 1-naphthyl and E is C(CF₃)₂ has a T_(g) ofabout 240° C. Typically, the compounds have a T_(g) of at least about50° C., preferably at least about 100° C.

Compounds of Formulae I and IV can be prepared via carbon-nitrogen bondformation methods known to one skilled in the art. For example, homo- orhetero-polymers can be produced by the reaction of one or more dihalomonomeric derivative(s) with equimolar amounts of one or more diamino(primary or secondary) monomeric unit(s) in the presence of copper,nickel or palladium catalysts. Alternatively, one or more monomerscontaining an amine and a halide as reactive groups can be employed.Typical conditions for Pd-catalyzed amination reactions are described inSadighi, J. P.; Singer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998,120, 4960; Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald,S. L. J. Org. Chem. 200, 65, 1158; Hartwig, J. F. Modern Arene Chemistry2002, 107-168. Editor: Astruc, D., Wiley-VCH Verlag GmbH & Co. KGaA,Weinheim, Germany. Typical conditions for Ni-catalyzed aminationreactions are described in Desmarets, C.; Schneider, R.; Fort, Y.Tetrahedon, 2001, 57, 6054; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem.Soc. 1997, 119, 4960. Typical conditions for Cu-catalyzed aminationreactions are described in Klapars, A.; Antilla, J. C.; Huang, X.;Buchwald, S. L. J. Am. Chem. Soc. 2001, 123, 7727.

For example, a diamine monomer E1 from Group 3, such asN,N′-diphenylbenzidine, is reacted with an equimolar amount of adihalide monomer A1, such as 4,4′-bromophenylisopropylidene, in presenceof a suitable base, such as NaO^(t)Bu, catalytic (less than oneequivalent) amount of a suitable palladium compound, such astris(dibenzylideneacetone) dipalladium, and a suitable ligand, such asP(^(t)Bu)₃. The polymerization is conducted at a temperature between 22°C. to 150° C. for 24 to 92 hours. The resulting polymer is then treatedwith an endcapping group, such as bromobenzene, and allowed to furtherreact for another 24 to 48 hours to produce a polymer of Formula IV,where R¹ is phenyl, E is C(CH₃)₂ and R²═R³ is phenyl.

In another example, monomer D1 from Group 2, such as4-(N-phenylamine)-4′-(bromophenyl)isopropylidene, can be polymerizedusing conditions described above to give a polymer of Formula IV, whereR¹ is phenyl, E is C(CH₃)₂ and R²═R³ is phenyl.

Compounds of Formula III can be prepared via carbon-carbon bondformation methods known to one skilled in the art. In one method,described in Yamamoto, Progress in Polymer Science, Vol. 17, p 1153(1992), the dihalo derivatives of the monomeric units are reacted with astoichiometric amount of a zerovalent nickel compound, such asbis(1,5-cyclooctadiene)nickel(0). In the second method, as described inColon et al., Journal of Polymer Science, Part A, Polymer chemistryEdition, Vol. 28, p. 367 (1990), the dihalo derivatives of the monomericunits are reacted with catalytic amounts of Ni(II) compounds in thepresence of stoichiometric amounts of a material capable of reducing thedivalent nickel ion to zerovalent nickel. Suitable materials includezinc, magnesium, calcium and lithium. In the third synthetic method, asdescribed in U.S. Pat. No. 5,962,631, and published PCT applicationWO00/53565, a dihalo derivative of one monomeric unit is reacted with aderivative of another monomeric unit having two reactive groups selectedfrom boronic acid, boronic acid esters, and boranes, in the presence ofa zerovalent palladium catalyst, such as tetrakis(triphenylphosphine)Pd.

For example, a polymeric composition of monomer C2 from Group 1, such as4,4′-N,N′-[(1-naphthyl)(4-chlorophenyl)]-(hexaflouroisopropylidene) isreacted with a stoichiometric amount of a zerovalent nickel compound,such as bis(1,5-cyclooctadiene)nickel(0), at a temperature between 22°C. to 150° C. for 24 to 92 hours.

For making electronic devices, including OLED devices, in oneembodiment, the compounds form films when deposited onto a transparentanode such as indium-doped tin oxide (ITO). The quality of the resultantfilm can be superficially judged by visual/microscopic inspection forsmoothness and defect density. With respect to OLEDs, it is preferredthat visually observed defects be minimal. Furthermore, film quality canbe measured by estimation of film thickness over several separate areasof the film using, for example, an optical ellipsometer or a mechanicalprofilometer; it is preferred that the films have substantially uniformthicknesses as measured in the different areas of the film.

For example, in one embodiment, compositions comprising at least one ofthe compounds of Formulae I, III, or IV can be in liquid form, such as adispersion, emulsion, or solution, in making electronic devices. Anexemplary process for making an electronic device, illustrated below foran organic light emitting diode, includes:

providing a liquid composition comprising a compound having a formulaselected from Formula (I) and Formula (III) as described hereinabove;

providing an anode;

disposing said liquid composition comprising said compound adjacent tosaid anode;

removing said liquid from said composition to produce at least one holetransport layer;

providing a material selected from a photoactive material and anelectrically active material;

disposing said material adjacent to said hole transport film; providingan electron transporter;

disposing said electron transporter adjacent to said emitter; and

providing a cathode adjacent to said electron transporter.

In one embodiment, the liquid composition comprises at least one solventfor the compound. A suitable solvent for a particular compound orrelated class of compounds can be readily determined by one skilled inthe art. For some applications, the compounds be dissolved innon-aqueous solvents. Such non-aqueous solvents can be relatively polar,such as C₁ to C₂₀ alcohols, ethers, and acid esters, or can berelatively non-polar such as C₁ to C₁₂ alkanes or aromatics.

Other suitable liquids mediums for use in making the liquid composition,either as a solution, emulsion, or dispersion comprising at least one ofthe new compounds, includes, but not limited to, chlorinatedhydrocarbons (such as methylene chloride, chloroform, chlorobenzene),aromatic hydrocarbons (such as substituted and non-substituted toluenesand xylenes, including trifluorotoluene), polar solvents (such astetrahydrofuran (THF), N-methyl pyrrolidone (NMP)) esters (such asethylacetate) alcohols (isopropanol), ketones (cyclopentanone) andmixtures thereof.

The compounds and composition comprising the compounds disclosed hereincan provide the electronic advantages of smaller molecules such astriarylamines, with the solution processability, film formingcapabilities, solubility properties, and thermal stability of polymericcompounds. In particular, it has been found that the compounds can beprovided in solution and used in solution processes to manufactureelectronic devices.

In one embodiment, the electronic devices for which the compounds areuseful are OLED devices. In contrast to known compounds such as NPD(N,N′-di(naphthalen-1-yl)-N,N′-diphenylbenzidine) and TPD(4,4′-bis[N-(3-methylphenyl)-N-phenylamino]biphenyl), which are commonlyused as hole transport materials in making OLED devices, using vapordeposition processes, the present compounds have improved thermalstability and can be selectively solubilized in common solvents. By“selectively solubilized” is meant that the compounds can be made to besoluble or substantially soluble in some solvents and insoluble orsubstantially insoluble in other solvents. For example, in using thecompounds to make electronic devices it is often desirable to providethe compound in a solvent in which the compound is soluble orsubstantially soluble, and deposit thereon another solvent in which thecompound is insoluble or substantially insoluble. Solubilization can beprovided or enhanced by variation of substituent groups on thecompounds.

In one embodiment, the compound is dissolved in a solvent in which thecompound is substantially soluble. The solution is then formed into athin film and dried by any of solution processing techniques. Theresultant film formed as the solvent evaporates is then further dried bybaking at elevated temperatures, including above the boiling point ofthe solvent, either in a vacuum of nitrogen atmosphere. The film is thensubjected to further processing by depositing a second solutioncontaining emissive layer materials on top of the pre-formed compoundfilm where the emissive materials are dissolved in a solvent in whichthe compound is substantially insoluble. By “substantially insoluble” ismeant that less than about 5 mg of the compound dissolves in 1 ml of thesolvent. However, solubilities greater than or less than 5 mg can beused and may be preferred for some applications. For example, a modestsolubility up to 10 mg/mL may result in a blurred or graded interfacebetween the HTM polymer of the present invention and the emissive layermaterials. Such blurring can have deleterious or beneficial effectsdepending upon the natures of the materials involved. Such blurring ofthe interface can result in improved charge transport across theinterface and substantially improved device performance or lifetime.

As will be recognized by one skilled in the art, the solubility of acompound is determined in part by substituent groups within thecompound. In particular, in the compounds disclosed herein, the natureof the group “E” in the compound can be varied in order to control thesolubility of a compound in a particular solvent or class of solvents.Thus, by varying the nature of the group “E”, a compound can be modifiedsuch that is more or less soluble in water or any given organicnon-aqueous solvent.

Also preferably, for making electronic devices, the compounds have arelatively low solubility, e.g., a solubility less than about 5 mg/mL,even about 2 mg/mL or less, in solvents that can be used to deposit anemissive layer film onto an electrode, which is typically a transparentanode such as ITO (indium doped tin oxide).

In one embodiment, there are provided electronic devices comprising atleast one layer containing at least one compound or composition asdisclosed herein. In one embodiment the layer is a charge transportlayer and in another embodiment, the layer is a hole transport layer.The new compounds or compositions comprising such compounds can be in aseparate layer, positioned between a photoactive layer and an electrode.Alternatively, a photoactive layer of an organic electronic device cancontain the composition. An example of an electronic device thatincludes at least one layer comprising at least one compound or acomposition is disclosed herein is shown in FIG. 1. The device 100 hasan anode layer 110 and a cathode layer 160. Adjacent to the anode is alayer 120 comprising hole transport material. Adjacent to the cathode isa layer 140 comprising an electron transport and/or anti-quenchingmaterial. Between the hole transport layer and the electron transportand/or anti-quenching layer is the photoactive layer 130. In theillustrated embodiment, the device has an optional additional transportlayer 150, next to the cathode. Layers 120, 130, 140, and 150 areindividually and collectively referred to as the active layers.

Depending upon the application of the device 100, the photoactive layer130 can be a light-emitting layer that is activated by an appliedvoltage (such as in a light-emitting diode or light-emittingelectrochemical cell), a layer of material that responds to radiantenergy and generates a signal with or without an applied bias voltage(such as in a photodetector). Examples of photodetectors includephotoconductive cells, photoresistors, photoswitches, phototransistors,and phototubes, and photovoltaic cells, as these terms are describe inMarkus, John, Electronics and Nucleonics Dictionary, 470 and 476(McGraw-Hill, Inc. 1966).

The compounds disclosed herein are particularly useful in the holetransport layer 120, and as a charge conducting host in the photoactivelayer, 130. The other layers in the device can be made of any materialsthat are known to be useful in such layers. The anode, 110, is anelectrode that is particularly efficient for injecting positive chargecarriers. It can be made of, for example, materials containing a metal,mixed metal, alloy, metal oxide or mixed-metal oxide, a conductingpolymer, or a combination or mixture thereof. Suitable metals includethe Group 11 metals, the metals in Groups 4, 5, and 6, and the Group8-10 transition metals. If the anode is to be light-transmitting,mixed-metal oxides of Group 12, 13 and 14 metals, such asindium-tin-oxide, are generally used. The anode 110 can also comprise anorganic material such as polyaniline, as described, for example, in“Flexible light-emitting diodes made from soluble conducting polymer,”Nature vol. 357, pp 477-479 (11 Jun. 1992). At least one of the anodeand cathode is preferably at least partially transparent to allow thegenerated light to be observed.

The photoactive layer 130 may typically be any organicelectroluminescent (“EL”) material, including, but not limited to,fluorescent dyes, fluorescent and phosphorescent metal complexes,conjugated polymers, and mixtures thereof. Examples of fluorescent dyesinclude, but are not limited to, pyrene, perylene, rubrene, derivativesthereof, and mixtures thereof. Examples of metal complexes include, butare not limited to, metal chelated oxinoid compounds, such astris(8-hydroxyquinolato)aluminum (Alq3); cyclometalated iridium andplatinum electroluminescent compounds, such as complexes of Iridium withphenylpyridine, phenylquinoline, or phenylpyrimidine ligands asdisclosed in Petrov et al., Published PCT Application WO 02/02714, andorganometallic complexes described in, for example, publishedapplications US 2001/0019782, EP 1191612, WO 02/15645, and EP 1191614;and mixtures thereof. Electroluminescent emissive layers comprising acharge carrying host material and a metal complex have been described byThompson et al., in U.S. Pat. No. 6,303,238, and by Burrows and Thompsonin published PCT applications WO 00/70655 and WO 01/41512.Electroluminescent emissive layers comprising a charge carrying hostmaterial and a phosphorescent platinum complex have been described byThompson et al., in U.S. Pat. No. 6,303,238, Bradley et al., in Synth.Met. (2001), 116 (1-3), 379-383, and Campbell et al., in Phys. Rev. B,Vol. 65 085210. Examples of conjugated polymers include, but are notlimited to poly(phenylenevinylenes), polyfluorenes,poly(spirobifluorenes), polythiophenes, poly(p-phenylenes), copolymersthereof, and mixtures thereof.

In one embodiment, the photoactive layer 130 comprises an organometalliccompound. These electroluminescent complexes can be used alone, or dopedinto charge-carrying hosts, as noted above. The compounds, in additionto being useful in the hole transport layer 120, electronic transportlayer 140/150 can also act as a charge carrying host for an emissivedopant in the photoactive layer 130 or otherwise part of the photoactivelayer.

Examples of electron transport materials which can be used in layer 140and/or layer 150 include metal chelated oxinoid compounds, such astris(8-hydroxyquinolato)aluminum (Alq3); and azole compounds such as2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) and3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), andmixtures thereof.

The cathode 160, is an electrode that is particularly efficient forinjecting electrons or negative charge carriers. The cathode can be anymetal or nonmetal having a lower work function than the anode. Materialsfor the cathode can be selected from alkali metals of Group 1 (e.g., Li,Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, includingthe rare earth elements and lanthanides, and the actinides. Materialssuch as aluminum, indium, calcium, barium, samarium and magnesium, aswell as combinations, can be used. Li-containing organometalliccompounds, LiF, and Li₂O can also be deposited between the organic layerand the cathode layer to lower the operating voltage.

It is known to have other layers in organic electronic devices. Forexample, there can be a layer (not shown) between the anode 110 and holetransport layer 120 to facilitate positive charge transport and/orband-gap matching of the layers, or to function as a protective layer.Layers that are known in the art can be used. In addition, any of theabove-described layers can be made of two or more layers. Alternatively,some or all of anode layer 110, the hole transport layer 120, theelectron transport layers 140 and 150, and cathode layer 160, may besurface treated to increase charge carrier transport efficiency. Thechoice of materials for each of the component layers is preferablydetermined by balancing the goals of providing a device with high deviceefficiency with device operational lifetime.

In one embodiment, the organic electronic device comprises at least onebuffer layer between the anode 110 and the hole transport layer 120. Theterm “buffer layer” as used herein, is intended to mean an electricallyconductive or semiconductive layer which can be used between an anodeand an active organic material. A buffer layer is believed to accomplishone or more function in an organic electronic device, including, but notlimited to planarization of the underlying layer, hole transport, holeinjection, scavenging of impurities, such as oxygen and metal ions,among other aspects to facilitate or to improve the performance of anorganic electronic device. The buffer layer can comprise at least onelayer having a hole transport material, which may be a small molecule,oligomer, or polymer. Examples of hole transport materials have beensummarized, for example, in Kirk-Othmer Encyclopedia of ChemicalTechnology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. Wang. Bothhole transporting molecules and polymers can be used. Commonly used holetransporting molecules are:N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]4,4′-diamine(TPD), 1,1-bis[(di-4-tolylamino) phenyl]cyclohexane (TAPC),N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine(ETPD), tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA),a-phenyl-4-N,N-diphenylaminostyrene (TPS), p-(diethylamino)benzaldehydediphenylhydrazone (DEH), triphenylamine (TPA),bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP),1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline (PPR or DEASP), 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane(DCZB), N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)4,4′-diamine(TTB), and porphyrinic compounds, such as copper phthalocyanine.Commonly used hole transporting polymers are polyvinylcarbazole,(phenylmethyl)polysilane, polythiophenes, and polyaniline. It is alsopossible to obtain hole transporting polymers by doping holetransporting molecules such as those mentioned above into polymers suchas polystyrene and polycarbonate.

In one embodiment, the buffer layer comprises an electrically conductingpolymer and a colloid-forming polymeric acid. As used herein, the term“colloid-forming” refers to substances that form minute particles whendispersed in aqueous solution, i.e., “colloid-forming” polymeric acidsare not water-soluble. In one embodiment, the conductive polymer isselected from polythiophenes, polyanilines, and polypyrroles. In oneembodiment, the colloid-forming polymeric acid is selected frompolymeric sulfonic acids, polymeric phosphoric acids, polymericphosphonic acids, polymeric carboxylic acids, polymeric acrylic acids,and mixtures thereof. In another embodiment, the colloid-formingpolymeric acid is a polymeric sulfonic acid which is fluorinated. Inanother embodiment, the colloid-forming polymeric sulfonic acidcomprises a perfluoroalkylenesulfonic acid.

In one embodiment, the buffer layer comprisespoly(3,4-ethylenedioxythiophene) (“PEDT”) andpoly(perfluoroethylenesulfonic acid) (“PFSA”). The buffer layer can beprepared from an aqueous dispersion of PEDT/PFSA, which in turn can beprepared by the oxidative polymerization of thiophene monomers in anaqeuous dispersion of the PFSA. The preparation of PFSA is well known,and has been described in, for example, U.S. Pat. No. 6,150,426.

Examples of other organic electronic devices that may benefit fromhaving one or more layers comprising at least one of the new compoundsand compositions described herein include, but are not limited to, (1)devices that convert electrical energy into radiation (e.g., alight-emitting diode, light emitting diode display, or diode laser), (2)devices that detect signals through electronics processes (e.g.,photodetectors (e.g., photoconductive cells, photoresistors,photoswitches, phototransistors, phototubes), IR detectors), (3) devicesthat convert radiation into electrical energy, (e.g., a photovoltaicdevice or solar cell), and (4) devices that include one or moreelectronic components that include one or more organic semi-conductorlayers (e.g., a transistor or diode). Other uses for the newcompositions include coating materials for memory storage devices,antistatic films, biosensors, electrochromic devices, energy storagedevices, and electromagnetic shielding applications.

It is understood that each functional layer may be made up of more thanone layer.

The devices can be prepared using a variety of techniques, includingsequentially vapor depositing the individual layers on a suitablesubstrate. Substrates such as glass and polymeric films can be used.Conventional vapor deposition techniques can be used, such as thermalevaporation, chemical vapor deposition, and the like. Alternatively, thelayer(s) comprising at least one composition can be applied usingsolution processing techniques. Combinations of vapor deposition andsolution coating of individual layers can be used. In general, thedifferent layers will have the following range of thicknesses: anode110, 500-5000 Å, preferably 1000-2000 Å; hole transport layer 120,50-2000 Å, preferably 200-1000 Å; photoactive layer 130, 10-2000 Å,preferably 100-1000 Å; electron transport layer 140 and 150, 50-2000 Å,preferably 100-1000 Å; cathode 160, 200-100000 Å, preferably 300-5000 Å.The location of the electron-hole recombination zone in the device, andthus the emission spectrum of the device, can be affected by therelative thickness of each layer. Thus the thickness of theelectron-transport layer should be chosen so that the electron-holerecombination zone is in the light-emitting layer. The desired ratio oflayer thicknesses will depend on the exact nature of the materials used.

In one embodiment, an electronic device is prepared in which at leasttwo organic layers are applied by solution processing. As used herein,the term “solution processing” is intended to mean processes thatinclude depositing from a liquid medium. The liquid medium can be in theform of a solution, a dispersion, an emulsion, or other forms. Typicalliquid deposition techniques include, but are not limited to, continuousdeposition techniques such as spin coating, gravure coating, curtaincoating, dip coating, slot-die coating, spray-coating, and continuousnozzle coating; and discontinuous liquid deposition techniques such asink jet printing, gravure printing, and screen printing. In oneembodiment, an electronic device is prepared in which at least twoorganic layers are applied by solution processing, and one of the layersapplied by solution processing is a photoactive layer comprising aphotoactive small molecule compound. As used herein, the term “smallmolecule” is intended to mean a compound having a molecular weight lessthan 2000. In one embodiment, the photoactive small molecule is selectedfrom a phosphorescent organometallic compound and a fluorescent dye. Inone embodiment, the photoactive small molecule is a blue luminescentmaterial. As used here, the term “blue luminescent material” is intendedto mean a material having photoluminescent and/or electroluminescentspectra with a maximum at 500 nm or less.

As used herein, the term “charge transport material” is intended to meancompounds or other compositions that can receive a charge from anelectrode and facilitate its movement through the thickness of thematerial with relatively high efficiency and small loss of charge. Holetransport materials are capable of receiving a positive charge from ananode and transporting it. Electron transport materials are capable ofreceiving a negative charge from a cathode and transporting it.

The term “compound” is intended to mean a substance whose moleculesconsist of unlike atoms and whose constituents cannot be separated byphysical means. The term “composition” is intended to be construedbroadly to include mixtures, solids (in a variety of forms such aspowders, flakes, pellets), or liquid formulations (wherein liquidcompositions include solutions, dispersions, emulsions) and eachcompositions includes at least one compound described herein.

The term “anti-quenching composition” is intended to mean a materialwhich prevents, retards, or diminishes both the transfer of energy andthe transfer of an electron to or from the excited state of thephotoactive layer to an adjacent layer.

The term “photoactive” refers to any material that exhibitselectroluminescence, photoluminescence, and/or photosensitivity.

The term “group” is intended to mean a part of a compound, such as asubstituent in an organic compound. Unless otherwise indicated, allgroups can be unsubstituted or substituted. The prefix “hetero”indicates that one or more carbon atoms have been replaced with adifferent atom. The prefix “fluoro” is intended to mean that one or moreof the hydrogen atoms attached to a carbon have been replaced with afluorine.

The term “alkyl” is intended to mean a group derived from an aliphatichydrocarbon having one point of attachment. The term “alkylene” isintended to mean a group derived from an aliphatic hydrocarbon andhaving two or more points of attachment. The term “alkenyl” is intendedto mean a group derived from a hydrocarbon having one or morecarbon-carbon double bonds and having one point of attachment. The term“alkynyl” is intended to mean a group derived from a hydrocarbon havingone or more carbon-carbon triple bonds and having one point ofattachment. The term “alkenylene” is intended to mean a group derivedfrom a hydrocarbon having one or more carbon-carbon double bonds andhaving two or more points of attachment. The term “alkynylene” isintended to mean a group derived from a hydrocarbon having one or morecarbon-carbon triple bonds and having two or more points of attachment.

The term “aryl” is intended to mean a group derived from an aromatichydrocarbon having one point of attachment. The term “arylalkylene” isintended to mean a group derived from an alkyl group having an arylsubstituent.

The term “arylene” is intended to mean a group derived from an aromatichydrocarbon having two points of attachment. The term “arylenealkylene”is intended to mean a group having both aryl and alkyl groups and havingone point of attachment on an aryl group and one point of attachment onan alkyl group. Unless otherwise indicated, all groups can beunsubstituted or substituted. The phrase “adjacent to,” when used torefer to layers in a device, does not necessarily mean that one layer isimmediately next to another layer. On the other hand, the phrase“adjacent R groups,” is used to refer to R groups that are next to eachother in a chemical formula (i.e., R groups that are on atoms joined bya bond).

The term “polymeric” or “polymer” is intended to encompass dimeric,oligomeric, homopolymeric and copolymeric species.

In addition, the IUPAC numbering system is used throughout, where thegroups from the Periodic Table are numbered from left to right as 1through 18 (CRC Handbook of Chemistry and Physics, 81^(st) Edition,2000).

The term “layer” or “film” refers to a coating covering a desired area.The area can be as large as an entire display, or as small as a specificfunction area such as a single sub-pixel. Films can be formed by anyconventional deposition technique.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, “the”, “a” or “an” are employed to describe elements andcomponents of the invention. This is done merely for convenience and togive a general sense of the invention. This description should be readto include one or at least one and the singular also includes the pluralunless it is obvious that it is meant otherwise.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Unless otherwise defined, allletter symbols in the figures represent atoms with that atomicabbreviation. Although methods and materials similar or equivalent tothose described herein can be used in the practice or testing of thepresent invention, suitable methods and materials are described below.

All publications, patent applications, patents, and other referencesmentioned herein are incorporated by reference in their entirety. Incase of conflict, the present specification, including definitions, willcontrol. In addition, the materials, methods, and examples areillustrative only and not intended to be limiting.

EXAMPLES

The following examples illustrate certain features and advantages of thepresent invention. They are intended to be illustrative of theinvention, but not limiting. All percentages are by weight, unlessotherwise indicated.

Example 1 Example 1. Polymer obtained from monomer 1.

Synthesis of monomer 1

Synthetic pathway to compound 1 is shown below.

All reactions were performed under a nitrogen atmosphere and thereaction flask was kept away from room light. To a toluene (anhydrous,300 mL) solution of 4,4′-(hexaflouroisopropylidene)dianiline (15.0 g),1-iodonaphthalene (22.9 g) and NaO^(t)Bu (12.95 g), a mixture oftris(dibenzylideneacetone) dipalladium (4.12 g) and P^(t)Bu₃ (2.28 g)was added. The resulting reaction mixture was stirred at roomtemperature for five days, after which it was filtered through a plug ofCelite® diatomaceous earth and washed with toluene (3×500 mL). Thevolatiles were removed by rotorary evaporation and the product waspurified by column chromatography (silica) using EtOAc/hexane (1:5)followed by crystallization from CH₂Cl_(2/)hexane to yield 1a in 67%yield (17.6 g).

A toluene (anhydrous, 480 mL) solution of 1a (17.6 g) was then mixedwith 1-chloro-4-iodobenzene (28.6 g), NaOtBu (8.65 g),tris(dibenzylideneacetone) dipalladium (2.20 g) and1,1′-bis(diphenyphosphino)ferrocene (2.66 g). The resulting reactionmixture was heated to 100 C for 48 hrs, after which it was filteredthrough a plug of Celite® diatomaceous earth and washed with toluene(4×250 mL). The volatiles were removed and the product was purified bycolumn chromatography (silica) using 1 L hexane followed by 15%CH₂Ch_(2/)hexane to give 1 as a white powder in 64% (15.4 g) yield.

Polymerization of 1

Bis(1,5-Cyclooctadiene)-nickel-(0) (3.334 g, 12.12 mmol) was added to aN,N-dimethylformamide (anhydrous, 15 mL) solution 2,2′-bipyridyl (1.893g, 12.12 mmol) and 1,5-cyclooctadiene (1.311 g, 12.12 mmol). Theresulting mixture was heated to 60 C for 30 min. The oil bathtemperature was then raised to 70 C and a toluene (anhydrous, 60 mL)solution of 1 (4.846 g ,6.0 mmol) was added rapidly to the stirringcatalyst mixture. The mixture was stirred at 70 C for 92 hours. Afterthe reaction mixture cooled to room temperature, it was poured, slowly,with vigorous stirring into 600 mL of an acetone/methanol (50:50 byvolume) mixture containing ˜30 mL conc. HCl. A light-gray fiberousprecipitate formed which partially broke-up during stirring. The mixturewas stirred for one hour and the solid was isolated by filtration. Thesolid was dissolved in ˜200 mL of chloroform and was poured withvigorous stirring, into 1200 mL of an acetone/methanol (50:50) mixturecontaining ˜30 mL conc. HCl. A light-gray fiberous mass formed, whichwas stirred for one hour and isolated by filtration. The solid was againdissolved in ˜200 mL chloroform, passed through a bed (˜3-4 cm) ofsilica gel 60. The filter bed was rinsed with ˜400 mL chloroform and thecombined chloroform solutions were concentrated to ˜150-200 mL andpoured, with vigorous stirring into 1600 mL of acetone/methanol (50:50by volume). A slightly off-white fiberous precipitate formed, whichstirred for one hour. The solid was isolated by filtration and was driedunder vacuum overnight. The solid was dissolved in tetrahydrofuran (250mL) and then slowly poured with vigorous stirring into 1500 mL of ethylacetate. The polymer precipitated out as a slightly off-white fiberousslurry. After stirring this mixture for one hour the precipirate wasisolated by filtration. This solid was re-dissolved on more time intetrahydrofuran (220 mL), filtered through a 0.2 um syringe filter (PTFEfilter membrane) and poured, slowly, with vigorous stirring into 1200 mLof methanol. The polymer precipitated out as a white fiberous slurry,which was isolated by filtration. After drying the resulting materialunder vacuum overnight 3.31 g (75%) of polymer was isolated. GPC (THF,room temperature): Mn=92,000; Mw=219,900; Mw/Mn=2.39.

Example 2 Synthesis of polymer 2

Synthetic pathway to polymer 2 is shown below.

All manipulations were performed under an atmosphere of nitrogen. A 200mL flask was charged with 4,4′-bromophenyl(hexaflouroisopropylidene)(3.64 g, 7.87 mmol), N,N-diphenylbezidine (2.67, 7.93 mmol), NaO^(t)Bu(2.29, 23.8 mmol), toluene (anhydrous, 95 mL), and a solution (10 mL,toluene) of tris(dibenzylideneacetone) dipalladium (0.363 g, 0.4 mmol)and P^(t)Bu₃ (0.482 g, 2.4 mmol). The resulting reaction mixture washeated to 100° C. for 48 hrs. Bromobenzene (2.74 g 17.4 mmol) was addedto the reaction mixture and allowed to stir for an additional 24 hours.After cooling to room temperature, the mixture was opened air anddiluted with 50% toluene/DMF to make a 1% solution (˜one liter) whichwas filtered through a one inch pad of Celite® diatomaceous earth. Theyellow filtrate was reduced in volume to ˜300 mL, after which it wasslowly added to a vigorously stirring solution of 50% MeOH/acetone(˜1800 mL). A precipitated formed, which was isolated by filtration anddried under vacuum to give 4.892 g (97%) of an off-white solid This wasdissolved in CHCL₃ to make a ˜8% solution which was added dropwise tovigorously stirring 6× volume of hexanes to produce a solid. Afterfiltering and drying, the resulting solid was dissolved in CHCl₃ (1%solution) and again precipitated in 6× volume of boiling acetonitrile.The precipitated was filtered and vacuum dried to yield 2.274 g of paleyellow powdery material. GPC (THF, room temperature): Mn =10,100; Mw=20,800; Mw/Mn =2.06.

Example 3 Synthesis of polymer 3

Synthetic pathway to polymer 3 is shown below.

All manipulations were performed under an atmosphere of nitrogen. A 200mL flask was charged with 4,4′-bromophenylisopropylidene (1.00 g, 2.82mmol), N,N-diphenylbezidine (0.96 g, 2.82 mmol), NaO^(t)Bu (0.85, 8.5mmol), toluene (anhydrous, 30 mL), and a solution (5 mL, toluene) oftris(dibenzylideneacetone) dipalladium (0.13 g, 0.14 mmol) and P^(t)Bu₃(0.17 g, 0.85 mmol). The resulting reaction mixture was heated to 100°C. for 48 hrs. Bromobenzene (0.98 g, 0.62 mmol) andtris(dibenzylideneacetone) dipalladium (0.032 g) and P^(t)Bu₃ (0.042 g).After additional 24 hrs, the reaction mixture was diluted with 50%toluene/DMF to make a 1% solution. After filtration the solvent wasevaporated and the resulting solid was dissolved with CHCl₃ (1 L) thenconcentrated to a viscous solution, which was precipitated in hexanesand filtered twice to remove all particles. The powder was driedovernight and then dissolved in chloroform and re-precipitated inboiling CH₃CN and filtered twice. After drying a pale-yellow powder wasisolated in 42% yield (0.629 g). Mn=3370; Mw=10,200; Mw/Mn=3.02.

Example 4 Synthesis of Dimer 4

All manipulations were carried under an atmosphere of nitrogen. ASchlenk flask was charged with N,N′-diphenyl-N-naphth-1-yl-benzidine(200 g, 432 mmol), 4,4′-bromophenyl(hexaflouroisopropylidene) (0.95 g,2.06 mmol), NaO^(t)Bu (0.623 g, 23.8 mmol), toluene (anhydrous, 40 mL),and a solution (5 mL, toluene) of tris(dibenzylideneacetone) dipalladium(0.198 g, 0.2 mmol) and P^(t)Bu₃ (0.262 g, 1.3 mmol). The mixture washeated to 100 C for 12 hrs. After cooling to room temperature thesolution was diluted with CH₂Cl₂ and filtered through Celite®diatomaceous earth. Evaporation of volatiles gave a brown solid that wasdissolved in a minimum of CH₂Cl₂ and precipitate from MeOH. Afterfiltration and drying the solid was purified by chromatography (silica,1:2 CH₂Cl_(2/)Hexanes. Further purification by crystallization(CH₂Cl_(2/)MeOH) yielded compound 4 as an off-white powder in 81 % yield(2.04 g). 1H NMR (CD₂Cl₂, 500 MHz): δ7.97 (d, 2H); 7.92 (d, 2H); 7.82(d, 2H); 7.49 (m, 8H); 7.40 (m, 8H); 7.30 (t, 4H); 7.24 (m, 8H); 7.15(m, 8H); 7.06 (m, 8H); 6.97 (t, 2H); 19F NMR (CD₂Cl_(2, 376.86) MHz):δ-64.66 (s).

Example 5 Synthesis of dimer 5

All manipulations were carried under an atmosphere of nitrogen. A roundbottom flask 4″,4′″-(hexaflouroisopropylidene)bix(4-phenoxyaniline)(10.08 g, 19.5 mmol), 1-iodonaphthalene (14.83 g, 58.4 mmol), NaO^(t)Bu(5.61 g, 58.4 mmol), toluene (anhydrous, 300 mL), and a solution (10 mL,toluene) of tris(dibenzylideneacetone) dipalladium (1.78 g, 1.95 mmol)and P^(t)Bu₃ (0.98 g, 4.87 mmol). The mixture was stirred at roomtemperature for four days. The resulting mixture was washed with water,and the organic layer was dried over MgSO₄. Removal of volatiles yieldeda brown oil which was purified by column chromatography using hexane(1.5 L) followed by hexane:EtOAc mixture of increasing polarity up topure EtOAc. The desired compound 5 was isolated as a white powder (1.0g). ¹H NMR (CD₂Cl₂, 500 MHz): δ 8.03 (d, 1H); 7.85 (d, 1H); 7.67 (d,1H); 7.43 (t, 1H); 7.30 (m, 3H); 7.17 (d, 1H); 6.88 (d, 1H); 6.83 (d,1H); 6.72 (d, 1H); ¹⁹F NMR (CD₂Cl₂, 376.86 MHz): δ −64.81 (s).

Example 6

In this example, a second sample of polymer 1 was synthesized.

Bis(1,5-Cyclooctadiene)-nickel-(0) (22.01 g, 80 mmol) was added to aN,N-dimethylformamide (anhydrous, 100 mL) solution 2,2′-bipyridyl (8.65g, 80 mmol) and 1,5-cyclooctadiene (1.311 g, 12.12 mmol). The resultingmixture was heated to 60 C for 30 min. The oil bath temperature was thenraised to 70 C and a toluene (anhydrous, 400 mL) solution of monomer 1from Example 1 (30.7 g, 38 mmol) was added rapidly to the stirringcatalyst mixture. The mixture was stirred at 70 C for 5 days. After thereaction mixture cooled to room temperature, it was poured, slowly, withvigorous stirring into ˜100 mL conc. HCl. The resulting mixture wasstirred for an hour and then added to 6 L of an acetone/methanol (50:50by volume) mixture containing ˜100 mL conc. HCl. A light-gray fiberousprecipitate formed which partially broke-up during stirring. The mixturewas stirred for 1.5 hours and the solid was isolated by filtration. Thesolid was dissolved in ˜1200 mL of chloroform and filtered through aplug of silica. The resulting solution was poured with vigorousstirring, into 6.4 L of an acetone/methanol (50:50) mixture containing˜320 mL conc. HCl. A light-gray fiberous mass formed, which was stirredfor one hour and isolated by filtration. The solid was again dissolvedin ˜1500 mL chloroform and precipitated as described above. The solidwas isolated by filtration and was dried under vacuum overnight. Thesolid was dissolved in chloroform (1200 mL) and then slowly poured withvigorous stirring into 3 L of ethyl acetate. The polymer precipitatedout as a white fiberous slurry, which was isolated by filtration. Afterdrying the resulting material under vacuum overnight 25.0 g (88%) ofpolymer was isolated. GPC (THF, room temperature): Mn=43,700;Mw=119,200; Mw/Mn=2.73.

Example 7

In this example an OLED is made by solution processing of the organiclayers, with a new polymer as the hole transport layer.

a. TCTA

TCTA is available commercially from H W Sands (Jupiter, Fla.). It can bemade as follows. In a dry box a 2-L round-bottomed flask was chargedwith tri(p-bromophenyl)amine, carbazole, Pd catalysttris(dibenzylideneacetone) dipalladium, di(t-butyl)o-biphenylphosphine,and toluene. To this stirring mixture, Na butoxide was added. Acondenser and septum were attached and the flask brought out of the drybox. The mixture was refluxed for 14 hours under nitrogen before beingdiluted with ether and the combined organic layers dried over magnesiumsulfate and concentrated to dryness affording a brown solid. The solidwas dissolved in hot toluene and precipitated out with the addition ofhexanes. The filtrate was a tan solid. This solid was dissolved in hottoluene and silica gel was added to the stirring mixture. The stirringmixture was filtered and concentrated until precipitate was visible.Hexanes were added to drive the precipitation, resulting in 14 g of atan fluffy solid. This sold was dissolved in 40 mL dichloromethane(“DCM”) and hexanes (2:1) and stirred until the volume was reduced to ⅓.This mixture was filtered affording a tan powder. This was furtherpurified by flash chromatography over silica using DCM:Hexane(2:1)−>DCM. Some fractions appeared pure by HPLC but were coloredyellow. These fractions were discarded and only colorless fractions pureby HPLC were kept. Final yield of the first crop was 5.2 g (15%).

b. PEDOT/PFSA

This was made according to the procedure in co-pending application Ser.No. 10/669494, filed Sep. 24, 2003. The Nafion® was a 12.5% (w/w)aqueous colloidal dispersion with an EW of 990. A 25% (w/w) dispersionwas made using a procedure similar to the procedure in U.S. Pat. No.6,150,426, Example 1, Part 2, except that the temperature isapproximately 270° C. This was diluted to form the 12.5% (w/w)dispersion.

In a 2000 mL reaction kettle are put 715 g of 12% solid content aqueousNafion® (82 mmol SO₃H groups) dispersion, 1530 g water, 0.5 g (0.98mmol) iron(III)sulfate (Fe₂(SO₄)₃), and 1011 μL of concentrated H₂SO₄(18.1 mmol). The reaction mixture is stirred for 15 min at 276 RPM usingan overhead stirrer fitted with a double stage propeller type blade,before addition of 8.84 g (37.1 mmol) sodium persulfate (Na₂S₂O₈) in 60mL of water, and 3.17 mL ethylenedioxythiophene (“EDT”, from H. C.Starck, (GmbH) is started from separate syringes using addition rate of4.2 mL/h for Na₂S₂O_(8/)water and 224μL/h for EDT while continuouslystirring at 276 RPM. The addition of EDT is accomplished by placing themonomer in a syringe connected to a Teflon® fluoropolymer tube thatleads directly into the reaction mixture. The end of the Teflon®fluoropolymer tube connecting the Na₂S₂O_(8/)water solution was placedabove the reaction mixture such tat the injection involved individualdrops falling from the end of the tube. The reaction is stopped 7 hoursafter the addition of monomer has finished by adding 170 g each ofLewatit MP62WS, a weakly basic anion exchange resin (from Bayer,Pittsburgh. PA) and Lewatit® MonoPlus S100, a strongly acidic, sodiumcation exchange resin (from Bayer, Pittsburgh, PA), and 225 g ofn-propanol to the reaction mixture and stirring it further for 7 hoursat 130 RPM. The ion-exchange resin is finally filtered from thedispersion using Whatman No. 54 filter paper. The pH of the dispersionis ˜4 and dried films derived from the dispersion have a conductivity of2.6×10⁻⁵ S/cm at room temperature.

c. TPBI

2,2′,2″-(1,3,5-phenylene)-tris[1-phenyl-1h-benzimidazole] (“TPBI”) canbe made according to the procedure in U.S. Pat. No. 5,645,948.

d. Device Fabrication

Patterned ITO substrates were cleaned with UV ozone for 10 minutes.Immediately after cooling, the aqueous dispersion of PEDT/Nafion® madeabove was spin-coated over the ITO surface to form a buffer layer. Thecathode leads were wiped clean with damp swabs and the substrates werethen baked in vacuo at 90° C. for 30 minutes. After cooling, thesubstrates were then spin-coated with a 1% w/v solution of Polymer 1,from Example 6, in toluene and then baked again at 130° C. for 30minutes. After cooling the substrates were spin-coated with a 1% w/vsolution of 1,3,6,8-tetraphenylpyrene-TCTA (purchased from Pfaltz &Bauer, Waterbury, Conn.) in chloroform (10:90). The cathode contactswere then wiped clean with toluene wetted swabs. The substrates weremasked and placed in a vacuum chamber. After pumping to a base pressureof 2×10⁻⁷ torr, a layer of TPBI was deposited by thermal evaporation toform the electron transport layer. This was followed by a layer of LiFand then Al, to form the cathode. The chamber was then vented tonitrogen, the masks were changed and the chamber evacuated again. Afterreaching a base pressure of 1×10⁻⁶ torr, a second layer of Al wasdeposited by thermal evaporation. The chamber was vented to nitrogen andthe devices were encapsulated using a glass lid and UV curable epoxy.These devices were then tested, demonstrating electroluminescence withefficiencies of 0.6 cd/A at 6 V, and blue light with cie coordinates ofx=0.165, y=0.102.

1. A compound having Formula (I):

wherein: n is an integer greater than 1; R¹ is selected from aryl,heteroaryl, fluoroaryl, and fluoroheteroaryl; R³ is selected from H andR¹; R² is selected from H, R¹, alkyl, fluoroalkyl, Cl, Br, I and anarylamino group of Formula (II),

wherein R⁴ is selected from aryl, H, R¹, alkyl, and fluoroalkyl; R⁵ andR⁶ are each independently selected from H, F, alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fluoroaryl, fluoroalkoxy, and fluoroaryloxy, andwherein R⁵ and R⁶ can, when taken together, form a ring; R⁷ is selectedfrom aryl, heteroaryl, fluoroaryl, and fluoroheteroaryl; and E isselected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of 1 to 20,(CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, and combinationsthereof, wherein R⁵ and R⁶ are each independently selected from H, F,alkyl, aryl, alkoxy, aryloxy, fluoroalkyl, fluoroaryl, fluoroalkoxy, andfluoroaryloxy and wherein R⁵ and R⁶ can, when taken together, form anon-aromatic ring, provided that when E is (CR⁵R⁶)_(m), and n is greaterthan 1 and m is 1, at least one of R⁵ and R⁶ is not hydrogen or ahydrocarbon.
 2. A compound of claim 1 having the Formula (IV):


3. A composition comprising at least one compound having the Formula ofclaim 1, where said composition is a liquid composition.
 4. A compoundhaving Formula (I):

wherein: R¹ phenyl; R² is an arylamino group of Formula (II),

wherein R⁴ is phenyl and R⁷ is naphthalenyl; R³=R¹; E is (CR⁵R⁶) and R⁵and R⁶ are each trifluromethyl; and n=1.